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Synlett 2018; 29(18): 2385-2389
DOI: 10.1055/s-0037-1610995
DOI: 10.1055/s-0037-1610995
letter
Iridium-Catalyzed Direct Cyclization of Aromatic Amines with Diols
Authors
This research was supported by Joint Research by Institute for Molecular Science (IMS) (IMS program No, 605), and Intra-university Joint Research Grant by Yamagata University Gender Equality Office. This work was partially supported by the Asahi Glass Foundation.
Weitere Informationen
Publikationsverlauf
Received: 27. August 2018
Accepted after revision: 30. August 2018
Publikationsdatum:
02. Oktober 2018 (online)
Abstract
We developed an environmentally friendly iridium-catalyzed direct cyclization of aromatic amines with diols that generates the corresponding N-heterocyclic compounds with water as the sole by-product. Thus, under conditions of 165 °C for 18 hours, the direct cyclization of N-methylanilines with 1,3-propanediol by using an IrCl3 catalyst with rac-BINAP as a ligand in mesitylene afforded the corresponding tetrahydroquinoline derivatives with yields ranging from 73 to 83%. Under similar reaction conditions, direct cyclization of anilines with 1,3-propanediol produced the corresponding tetrahydrobenzoquinolizine derivatives with yields ranging from 26 to 76%.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610995.
- Supporting Information (PDF)
-
References and Notes
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- 12 General Procedure and Characterization Data: Ir-catalyzed direct cyclization of 3-fluoro-aniline (4e) with 1,3-propanediol (2a) (Table 3, entry 5): To a vial was added 3-fluoroaniline (111.1 mg, 1.0 mmol), IrCl3·3H3O (11.5 mg, 5.0 mol%), and rac-BINAP (30.4 mg, 7.5 mol%) under air. Furthermore, mesitylene (0.5 mL) and then 1,3-propanediol (98.9 mg, 1.3 mmol) were added and the reaction mixture was stirred at 165 °C for 18 h. After the reaction, the resulting mixture was diluted with hexane. Then, the reaction mixture was filtrated with a filter paper and concentrated in vacuo. The resulting residue was purified by flash column chromatography on SiO2 ( t BuOMe/hexane 1:15) to yield 2,3,6,7-tetrahydro-8-fluoro-1H,5H-benzo[ij]quinolizine (5e) in 59% yield (73.2 mg) as a pale yellow solution. 1H NMR (500 MHz, CDCl3): δ = 1.92−1.98 (m, 4 H), 2.68−2.72 (m, 4 H), 3.09−3.12 (m, 4 H), 6.24 (t, J HF = 8.8 Hz, 1 H), 6.70 (t, J HF = 7.5 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 20.3 (d, 3 J CF = 5.9 Hz), 21.3, 22.2, 27.3, 49.6, 50.0, 102.0 (d, 2 J CF = 22.9 Hz), 108.5 (d, 2 J CF = 21.7 Hz), 116.8 (d, 4 J CF = 2.4 Hz), 126.8 (d, 3 J CF = 10.8 Hz), 144.1, (d, 3 J CF = 8.4 Hz), 159.7 (d, 1 J CF = 241.3 Hz) ppm. 19F-NMR (470 MHz, CDCl3): δ = −124.2 ppm. HRMS: m/z calcd for C12H14FN [M]+: 191.1110; found: 191.1110.
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- 14 The reaction of 4a with 1,4-butanediol (2c) resulted in a double N-alkylation to afford 1-phenylpyrrolidine in 76% yield (see Supporting Information).
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